CN109207093A - A kind of formaldehydeless polyethylene house ornamentation binder and preparation method thereof - Google Patents
A kind of formaldehydeless polyethylene house ornamentation binder and preparation method thereof Download PDFInfo
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- CN109207093A CN109207093A CN201811061919.6A CN201811061919A CN109207093A CN 109207093 A CN109207093 A CN 109207093A CN 201811061919 A CN201811061919 A CN 201811061919A CN 109207093 A CN109207093 A CN 109207093A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention is related to a kind of formaldehydeless polyethylene house ornamentation binder, including following raw material components: modified poly ethylene and silicone modified polyethylene, modified poly ethylene is by polyethylene, terpene resin, natural rubber, modified tributyl 2-acetylcitrate, maleic anhydride and modified polyacrylate resin reaction are made, modified tributyl 2-acetylcitrate is by tributyl 2-acetylcitrate, 10X molecular sieve, A-171 silane coupling agent, tributyl citrate and the reaction of mesoporous aluminum oxide are made, modified polyacrylate resin is by acrylic acid, acrylonitrile, Isooctyl acrylate monomer, methyl methacrylate, benzoyl peroxide, maleic anhydride and styrene reaction are made, silicone modified polyethylene is by polyethylene, maleic anhydride, silicone master batch HNC-MB50, acrylic acid, 2-ethyl hexyl acrylate, azodiisobutyronitrile and third The reaction of alkene nitrile is made.The invention has excellent formaldehydeless property and adhesion strength.
Description
Technical field
The invention is related to a kind of formaldehydeless polyethylene house ornamentation binder and preparation method thereof.
Background technique
Polythene material possesses excellent nontoxic, low-density, light resistance, translucency, low water vapor permeability, ageing-resistant xanthochromia
The performances such as energy, processing performance, mechanical strength.Polyethylene is widely used in household plastic articles, life antistaling film, family
With fields such as insulated wire cable, home-use water supply and sewerage pipeline, anti-oxidant sealed plastic inner lining films.
Currently, polythene material needs further to be promoted in adhesion strength.The invention is changed using modified poly ethylene and silicone
Property polyethylene be prepared for formaldehydeless polyethylene house ornamentation binder, the formaldehydeless polyethylene house ornamentation binder of this method preparation has excellent
Different formaldehydeless property and adhesion strength.
Summary of the invention
A kind of preparation method for being designed to provide formaldehydeless polyethylene house ornamentation binder of the invention, this method is by changing
Become reactant feed and technology mode, the material of preparation has excellent formaldehydeless property and adhesion strength.
To achieve the goals above, the technical solution of the invention is as follows.
A kind of formaldehydeless polyethylene house ornamentation binder and preparation method thereof, specifically includes the following steps: (1), by polyethylene,
Maleic anhydride, silicone master batch HNC-MB50, acrylic acid, 2-ethyl hexyl acrylate, azodiisobutyronitrile and acrylonitrile are according to quality
Portion rate is that 69:9~17:14~20:2~7:9~16:0.3~1:2~5 are added in reaction kettle, mixing speed 90r/
Min reacts 30min under the conditions of 50 DEG C of maintenance system temperature, by temperature of reaction kettle be warming up to 78~87 DEG C of reactions 45~
Temperature of reaction kettle is warming up to 95 DEG C of heat preservation 1h by 60min, and product washs 2 times through 500mL EtOH Sonicate, dry, and product is shifted
Into extruder, in 173~180 DEG C of extruding pelletizations, silicone modified polyethylene is obtained；(2), by acrylic acid, acrylonitrile, propylene
The different monooctyl ester of acid, methyl methacrylate, benzoyl peroxide, maleic anhydride and styrene are 6:2 according to mass parts ratio
~5:14~21:1~3:0.3~1:3~7:1~2 are added in reaction kettle, mixing speed 230r/min, maintenance system temperature
45min is reacted under the conditions of 80~85 DEG C of degree, product is transferred in hydrothermal reaction kettle, maintaining hydrothermal temperature is 95~110
DEG C 1~3h of hydro-thermal reaction, product wash 2 times through 500mL EtOH Sonicate, dry, obtain modified polyacrylate resin；(3), will
10X molecular sieve and mesoporous aluminum oxide are added in ball mill according to mass parts ratio for 11~17:8~16, drum speed
For 23r/min, barrel temperature is 40 DEG C of ball-milling reaction 45min, is the second of 30:8~14:9~15 by product and mass parts ratio
Acyl tributyl citrate, A-171 silane coupling agent and tributyl citrate are added in hydrothermal reaction kettle, maintain hydro-thermal reaction temperature
Degree is 93~108 DEG C of 35~50min of hydro-thermal reaction, and product is done through 500mL alcohol dipping 1min in 45 DEG C, -0.06MPa vacuum
Dry 6min is to get to modified tributyl 2-acetylcitrate；(4), by polyethylene, terpene resin, natural rubber, modified acetyl lemon
Sour tributyl, maleic anhydride and modified polyacrylate resin are 83:39~50:21~27:22 according to mass parts ratio
~31:17~25:23~30 are added in high-speed mixer, with high-speed mixer 175~181 DEG C of hybrid reactions 2 of temperature~
6min, with extruder 177~183 DEG C of extruding pelletizations of temperature to get arrive modified poly ethylene；(5), by modified poly ethylene and silicone
Modified poly ethylene according to mass parts ratio be 81:21~29 be added in high-speed mixer, with high-speed mixer temperature 177~
183 DEG C of 1~5min of hybrid reaction, with extruder 179~185 DEG C of extruding pelletizations of temperature to get arrive formaldehydeless polyethylene house ornamentation
Binder.
The preparation method of formaldehydeless polyethylene house ornamentation binder described in the invention, including the following steps:
(1), by polyethylene, maleic anhydride, silicone master batch HNC-MB50, acrylic acid, 2-ethyl hexyl acrylate, azodiisobutyronitrile
It is added in reaction kettle according to mass parts ratio for 69:9~17:14~20:2~7:9~16:0.3~1:2~5 with acrylonitrile,
Mixing speed is 90r/min, reacts 30min under the conditions of 50 DEG C of maintenance system temperature, temperature of reaction kettle is warming up to 78~87
DEG C 45~60min of reaction, is warming up to 95 DEG C of heat preservation 1h for temperature of reaction kettle, and product washs 2 times through 500mL EtOH Sonicate, dries,
Product is transferred in extruder, in 173~180 DEG C of extruding pelletizations, obtains silicone modified polyethylene；The silicone master batch
The purpose of HNC-MB50,2-ethyl hexyl acrylate and acrylonitrile are in order to improve the adhesion strength of polythene material.
(2), by acrylic acid, acrylonitrile, Isooctyl acrylate monomer, methyl methacrylate, benzoyl peroxide, maleic two
Acid anhydrides and styrene are that 6:2~5:14~21:1~3:0.3~1:3~7:1~2 are added to reaction kettle according to mass parts ratio
In, mixing speed 230r/min reacts 45min under the conditions of 80~85 DEG C of maintenance system temperature, and it is anti-that product is transferred to hydro-thermal
It answers in kettle, maintenance hydrothermal temperature is 95~110 DEG C of 1~3h of hydro-thermal reaction, and product washs 2 times through 500mL EtOH Sonicate,
It is dry, obtain modified polyacrylate resin；The purpose of the maleic anhydride is in order to improve the compatibility between raw material.
It (3), is that 11~17:8~16 are added to ball milling according to mass parts ratio by 10X molecular sieve and mesoporous aluminum oxide
In machine, drum speed 23r/min, barrel temperature is 40 DEG C of ball-milling reaction 45min, by product and mass parts ratio be 30:8~
Tributyl 2-acetylcitrate, A-171 silane coupling agent and the tributyl citrate of 14:9~15 are added in hydrothermal reaction kettle, dimension
Holding hydrothermal temperature is 93~108 DEG C of 35~50min of hydro-thermal reaction, product through 500mL alcohol dipping 1min, in 45 DEG C ,-
0.06MPa is dried in vacuo 6min to get modified tributyl 2-acetylcitrate is arrived；The 10X molecular sieve and mesoporous three oxidation two
The purpose of aluminium is in order to adsorb raw material.
(4), by polyethylene, terpene resin, natural rubber, modified tributyl 2-acetylcitrate, maleic anhydride and change
Property polyacrylate resin according to mass parts ratio be 83:39~50:21~27:22~31:17~25:23~30 be added to height
In fast mixing machine, with high-speed mixer in 175~181 DEG C of 2~6min of hybrid reaction of temperature, with extruder in temperature 177~183
DEG C extruding pelletization is to get arriving modified poly ethylene；The purpose of the modification tributyl 2-acetylcitrate is in order to improve polyethylene material
The flexibility of material.
(5), modified poly ethylene and silicone modified polyethylene high speed is added to according to mass parts ratio for 81:21~29 to mix
In conjunction machine, with high-speed mixer in 177~183 DEG C of 1~5min of hybrid reaction of temperature, squeezed with extruder at 179~185 DEG C of temperature
It is granulated out to get formaldehydeless polyethylene house ornamentation binder is arrived.
Invention has the beneficial effects that:
1, silicone master batch HNC-MB50,2-ethyl hexyl acrylate and acrylonitrile carry out surface aggregate modification to polythene material, synthesis
Polymer can improve the adhesive property of polythene material, by physical modification, silicone master batch HNC-MB50, propylene is misery
Ester and acrylonitrile polymer are dispersed in polythene material, improve the adhesion strength of polyethylene fitment material for family；
2, the polymer of acrylic acid, acrylonitrile and Isooctyl acrylate monomer monomer has lower glass transition temperatures and high bonding strong
Degree, maleic anhydride is introduced into polyacrylate resin structure, using the chemical group in maleic anhydride to poly-
Vinyl Graft is modified, improves the compatibility between polyacrylate resin and polyethylene；The polyacrylate resin of preparation is because having
Excellent compatibility and adhesion strength can improve the adhesion strength of polyethylene fitment material for family；
3,10X molecular sieve and mesoporous aluminum oxide have porous structure, in hydro-thermal state, tributyl 2-acetylcitrate, A-
171 silane coupling agents and tributyl citrate are attracted in 10X molecular sieve and mesoporous aluminum oxide structure, reduce acetyl lemon
Lemon acid tributyl, A-171 silane coupling agent and tributyl citrate material volatility and improve its storage stability；
4, modified tributyl 2-acetylcitrate can release three fourth of acetyl tributyl citrate of its absorption during PE Processing
Ester, A-171 silane coupling agent and tributyl citrate plasticizer improve the flexibility and glass transition temperature of polythene material
Degree；Terpene resin, natural rubber and modified polyacrylate resin have lower glass transition temperature, can substantially change poly-
The glass transition temperature of vinyl material；The modified poly ethylene of preparation can be obviously improved the adhesion strength of polyethylene fitment material for family；
5, modified poly ethylene and silicone modified polyethylene synergistic effect under, because in used raw material and its synthesis process not
Containing formaldehyde, therefore, assign formaldehydeless polyethylene house ornamentation binder excellent formaldehydeless and adhesion strength.
Specific embodiment
A specific embodiment of the invention is described below with reference to embodiment, to better understand the present invention.This
It is a little that examples are only for illustrating the present invention and not for limiting the scope of the present invention.Actual conditions are not specified in lower example embodiment
Experimental method, usually according to this field normal condition or the condition suggested according to manufacturer；Used raw material, reagent etc.,
It unless otherwise specified, is the raw materials and reagents that can be obtained from commercial sources such as conventional markets.Those skilled in the art is at this
The variation and replacement of any unsubstantiality done on the basis of invention belong to scope of the present invention.
Embodiment 1
A kind of formaldehydeless polyethylene house ornamentation binder, preparation method includes the following steps:
(1), 69 parts of polyethylene, 13 parts of maleic anhydrides, 17 parts of silicone master batch HNC-MB50,3.9 parts of acrylic acid, 11.3 are weighed
Part 2-ethyl hexyl acrylate, 0.4 part of azodiisobutyronitrile and 3.6 parts of acrylonitrile are added in reaction kettle, mixing speed 90r/min,
30min is reacted under the conditions of 50 DEG C of maintenance system temperature, temperature of reaction kettle is warming up to 82 DEG C of reaction 50min, kettle temperature will be reacted
Degree is warming up to 95 DEG C of heat preservation 1h, and product washs 2 times through 500mL EtOH Sonicate, dry, product is transferred in extruder, in 177
DEG C extruding pelletization, obtains silicone modified polyethylene；
(2), 6 parts of acrylic acid, 3.1 parts of acrylonitrile, 18 parts of Isooctyl acrylate monomers, 1.3 parts of methyl methacrylates, 0.4 part are weighed
Benzoyl peroxide, 5.5 parts of maleic anhydrides and 1.2 parts of styrene are added in reaction kettle, mixing speed 230r/min,
45min is reacted under the conditions of 82 DEG C of maintenance system temperature, product is transferred in hydrothermal reaction kettle, maintenance hydrothermal temperature is
103 DEG C of hydro-thermal reaction 2h, product wash 2 times through 500mL EtOH Sonicate, dry, obtain modified polyacrylate resin；
(3), 13 parts of 10X molecular sieves are weighed and 11 parts of mesoporous aluminum oxides are added in ball mill, drum speed 23r/
Min, barrel temperature are 40 DEG C of ball-milling reaction 45min, and product and 30 parts of tributyl 2-acetylcitrates, 9.8 parts of A-171 silane is even
Connection agent and 12 parts of tributyl citrate are added in hydrothermal reaction kettle, and maintenance hydrothermal temperature is 105 DEG C of hydro-thermal reactions
40min, product are dried in vacuo 6min through 500mL alcohol dipping 1min, in 45 DEG C, -0.06MPa to get modified acetyl lemon is arrived
Sour tributyl；
(4), 83 parts of polyethylene, 43 parts of terpene resins, 25 parts of natural rubbers, 27 parts of modified tributyl 2-acetylcitrates, 22 are weighed
Part maleic anhydride and 26 parts of modified polyacrylate resins are added in high-speed mixer, with high-speed mixer in temperature
178 DEG C of hybrid reaction 3min, with extruder 180 DEG C of extruding pelletizations of temperature to get arrive modified poly ethylene；
(5), 81 parts of modified poly ethylenes are weighed and 26 parts of silicone modified polyethylene are added in high-speed mixer, use high-speed mixer
In 178 DEG C of hybrid reaction 2min of temperature, with extruder in 181 DEG C of extruding pelletizations of temperature to get viscous to formaldehydeless polyethylene house ornamentation
Tie agent.
Embodiment 2
A kind of formaldehydeless polyethylene house ornamentation binder, preparation method includes the following steps:
(1), 69 parts of polyethylene, 9 parts of maleic anhydrides, 14 parts of silicone master batch HNC-MB50,2 parts of acrylic acid, 9 parts of propylene are weighed
Misery ester, 0.3 part of azodiisobutyronitrile and 2 parts of acrylonitrile are added in reaction kettle, mixing speed 90r/min, maintenance system
30min is reacted under the conditions of 50 DEG C of temperature, temperature of reaction kettle is warming up to 78 DEG C of reaction 60min, temperature of reaction kettle is warming up to
95 DEG C of heat preservation 1h, product wash 2 times through 500mL EtOH Sonicate, dry, and product is transferred in extruder, squeeze out in 173 DEG C
It is granulated, obtains silicone modified polyethylene；
(2), 6 parts of acrylic acid, 2 parts of acrylonitrile, 14 parts of Isooctyl acrylate monomers, 1 part of methyl methacrylate, 0.3 part of peroxide are weighed
Change benzoyl, 3 parts of maleic anhydrides and 1 part of styrene to be added in reaction kettle, mixing speed 230r/min, maintenance system
45min is reacted under the conditions of 80 DEG C of temperature, product is transferred in hydrothermal reaction kettle, maintenance hydrothermal temperature is 95 DEG C of hydro-thermals
3h is reacted, product washs 2 times through 500mL EtOH Sonicate, and it is dry, obtain modified polyacrylate resin；
(3), 11 parts of 10X molecular sieves are weighed and 8 parts of mesoporous aluminum oxides are added in ball mill, drum speed 23r/min,
Barrel temperature is 40 DEG C of ball-milling reaction 45min, by product and 30 parts of tributyl 2-acetylcitrates, 8 parts of A-171 silane coupling agents and
9 parts of tributyl citrate are added in hydrothermal reaction kettle, and maintenance hydrothermal temperature is 93 DEG C of hydro-thermal reaction 50min, product warp
500mL alcohol dipping 1min is dried in vacuo 6min in 45 DEG C, -0.06MPa to get modified tributyl 2-acetylcitrate is arrived；
(4), 83 parts of polyethylene, 39 parts of terpene resins, 21 parts of natural rubbers, 22 parts of modified tributyl 2-acetylcitrates, 17 are weighed
Part maleic anhydride and 23 parts of modified polyacrylate resins are added in high-speed mixer, with high-speed mixer in temperature
175 DEG C of hybrid reaction 6min, with extruder 177 DEG C of extruding pelletizations of temperature to get arrive modified poly ethylene；
(5), 81 parts of modified poly ethylenes are weighed and 21 parts of silicone modified polyethylene are added in high-speed mixer, use high-speed mixer
In 177 DEG C of hybrid reaction 5min of temperature, with extruder in 179 DEG C of extruding pelletizations of temperature to get viscous to formaldehydeless polyethylene house ornamentation
Tie agent.
Embodiment 3
A kind of formaldehydeless polyethylene house ornamentation binder, preparation method includes the following steps:
(1), 69 parts of polyethylene, 17 parts of maleic anhydrides, 20 parts of silicone master batch HNC-MB50,7 parts of acrylic acid, 16 part third are weighed
Olefin(e) acid monooctyl ester, 1 part of azodiisobutyronitrile and 5 parts of acrylonitrile are added in reaction kettle, mixing speed 90r/min, maintenance system
30min is reacted under the conditions of 50 DEG C of temperature, temperature of reaction kettle is warming up to 87 DEG C of reaction 45min, temperature of reaction kettle is warming up to
95 DEG C of heat preservation 1h, product wash 2 times through 500mL EtOH Sonicate, dry, and product is transferred in extruder, squeeze out in 180 DEG C
It is granulated, obtains silicone modified polyethylene；
(2), 6 parts of acrylic acid, 5 parts of acrylonitrile, 21 parts of Isooctyl acrylate monomers, 3 parts of methyl methacrylates, 1 part of peroxidating are weighed
Benzoyl, 7 parts of maleic anhydrides and 2 parts of styrene are added in reaction kettle, mixing speed 230r/min, maintenance system temperature
45min is reacted under the conditions of 85 DEG C of degree, product is transferred in hydrothermal reaction kettle, maintenance hydrothermal temperature is 110 DEG C of hydro-thermals
1h is reacted, product washs 2 times through 500mL EtOH Sonicate, and it is dry, obtain modified polyacrylate resin；
(3), 17 parts of 10X molecular sieves are weighed and 16 parts of mesoporous aluminum oxides are added in ball mill, drum speed 23r/
Min, barrel temperature are 40 DEG C of ball-milling reaction 45min, and product and 30 parts of tributyl 2-acetylcitrates, 14 parts of A-171 silane is even
Connection agent and 15 parts of tributyl citrate are added in hydrothermal reaction kettle, and maintenance hydrothermal temperature is 108 DEG C of hydro-thermal reactions
35min, product are dried in vacuo 6min through 500mL alcohol dipping 1min, in 45 DEG C, -0.06MPa to get modified acetyl lemon is arrived
Sour tributyl；
(4), 83 parts of polyethylene, 50 parts of terpene resins, 27 parts of natural rubbers, 31 parts of modified tributyl 2-acetylcitrates, 25 are weighed
Part maleic anhydride and 30 parts of modified polyacrylate resins are added in high-speed mixer, with high-speed mixer in temperature
181 DEG C of hybrid reaction 2min, with extruder 183 DEG C of extruding pelletizations of temperature to get arrive modified poly ethylene；
(5), 81 parts of modified poly ethylenes are weighed and 29 parts of silicone modified polyethylene are added in high-speed mixer, use high-speed mixer
In 183 DEG C of hybrid reaction 1min of temperature, with extruder in 185 DEG C of extruding pelletizations of temperature to get viscous to formaldehydeless polyethylene house ornamentation
Tie agent.
Embodiment 4
A kind of formaldehydeless polyethylene house ornamentation binder, preparation method includes the following steps:
(1), weigh 69 parts of polyethylene, 9.2 parts of maleic anhydrides, 14.5 parts of silicone master batch HNC-MB50,2.3 parts of acrylic acid,
9.1 parts of 2-ethyl hexyl acrylates, 0.4 part of azodiisobutyronitrile and 2.2 parts of acrylonitrile are added in reaction kettle, mixing speed 90r/
Min reacts 30min under the conditions of 50 DEG C of maintenance system temperature, temperature of reaction kettle is warming up to 79 DEG C of reaction 46min, will be reacted
Kettle temperature degree is warming up to 95 DEG C of heat preservation 1h, and product washs 2 times through 500mL EtOH Sonicate, dry, and product is transferred in extruder,
In 174 DEG C of extruding pelletizations, silicone modified polyethylene is obtained；
(2), 6 parts of acrylic acid, 2.2 parts of acrylonitrile, 14.5 parts of Isooctyl acrylate monomers, 1.1 parts of methyl methacrylates, 0.4 are weighed
Part benzoyl peroxide, 3.2 parts of maleic anhydrides and 1.2 parts of styrene are added in reaction kettle, mixing speed 230r/
Min reacts 45min under the conditions of 81 DEG C of maintenance system temperature, product is transferred in hydrothermal reaction kettle, maintains hydro-thermal reaction temperature
Degree is 96 DEG C of hydro-thermal reaction 1.3h, and product washs 2 times through 500mL EtOH Sonicate, dry, obtains modified polyacrylate resin；
(3), 11.6 parts of 10X molecular sieves are weighed and 8.3 parts of mesoporous aluminum oxides are added in ball mill, drum speed 23r/
Min, barrel temperature are 40 DEG C of ball-milling reaction 45min, and product and 30 parts of tributyl 2-acetylcitrates, 8.2 parts of A-171 silane is even
Connection agent and 9.5 parts of tributyl citrate are added in hydrothermal reaction kettle, and maintenance hydrothermal temperature is 94 DEG C of hydro-thermal reactions
36min, product are dried in vacuo 6min through 500mL alcohol dipping 1min, in 45 DEG C, -0.06MPa to get modified acetyl lemon is arrived
Sour tributyl；
(4), 83 parts of polyethylene, 39.7 parts of terpene resins, 21.8 parts of natural rubbers, 23 parts of three fourths of modified acetyl tributyl citrate are weighed
Ester, 17.7 parts of maleic anhydrides and 24 parts of modified polyacrylate resins are added in high-speed mixer, use high-speed mixer
In 176 DEG C of hybrid reaction 2.5min of temperature, with extruder in 178 DEG C of extruding pelletizations of temperature to get arriving modified poly ethylene；
(5), 81 parts of modified poly ethylenes are weighed and 22 parts of silicone modified polyethylene are added in high-speed mixer, use high-speed mixer
In 178 DEG C of hybrid reaction 1.5min of temperature, with extruder in 180 DEG C of extruding pelletizations of temperature to get arriving formaldehydeless polyethylene house ornamentation
Binder.
Embodiment 5
A kind of formaldehydeless polyethylene house ornamentation binder, preparation method includes the following steps:
(1), weigh 69 parts of polyethylene, 10.3 parts of maleic anhydrides, 15.5 parts of silicone master batch HNC-MB50,3.5 parts of acrylic acid,
10.8 parts of 2-ethyl hexyl acrylates, 0.5 part of azodiisobutyronitrile and 3 parts of acrylonitrile are added in reaction kettle, mixing speed 90r/
Min reacts 30min under the conditions of 50 DEG C of maintenance system temperature, temperature of reaction kettle is warming up to 81 DEG C of reaction 49min, will be reacted
Kettle temperature degree is warming up to 95 DEG C of heat preservation 1h, and product washs 2 times through 500mL EtOH Sonicate, dry, and product is transferred in extruder,
In 175 DEG C of extruding pelletizations, silicone modified polyethylene is obtained；
(2), 6 parts of acrylic acid, 3.3 parts of acrylonitrile, 16 parts of Isooctyl acrylate monomers, 1.8 parts of methyl methacrylates, 0.5 part are weighed
Benzoyl peroxide, 4.5 parts of maleic anhydrides and 1.4 parts of styrene are added in reaction kettle, mixing speed 230r/min,
45min is reacted under the conditions of 83 DEG C of maintenance system temperature, product is transferred in hydrothermal reaction kettle, maintenance hydrothermal temperature is
99 DEG C of hydro-thermal reaction 1.8h, product wash 2 times through 500mL EtOH Sonicate, dry, obtain modified polyacrylate resin；
(3), 13.5 parts of 10X molecular sieves are weighed and 9.6 parts of mesoporous aluminum oxides are added in ball mill, drum speed 23r/
Min, barrel temperature are 40 DEG C of ball-milling reaction 45min, and product and 30 parts of tributyl 2-acetylcitrates, 9.9 parts of A-171 silane is even
Connection agent and 11.2 parts of tributyl citrate are added in hydrothermal reaction kettle, and maintenance hydrothermal temperature is 99 DEG C of hydro-thermal reactions
38min, product are dried in vacuo 6min through 500mL alcohol dipping 1min, in 45 DEG C, -0.06MPa to get modified acetyl lemon is arrived
Sour tributyl；
(4), weigh 83 parts of polyethylene, 43 parts of terpene resins, 23 parts of natural rubbers, 23.9 parts of modified tributyl 2-acetylcitrates,
19.8 parts of maleic anhydrides and 25 parts of modified polyacrylate resins are added in high-speed mixer, with high-speed mixer in temperature
Spend 179 DEG C of hybrid reaction 3min, with extruder 179 DEG C of extruding pelletizations of temperature to get arrive modified poly ethylene；
(5), 81 parts of modified poly ethylenes are weighed and 23 parts of silicone modified polyethylene are added in high-speed mixer, use high-speed mixer
In 179 DEG C of hybrid reaction 3min of temperature, with extruder in 182 DEG C of extruding pelletizations of temperature to get viscous to formaldehydeless polyethylene house ornamentation
Tie agent.
Embodiment 6
A kind of formaldehydeless polyethylene house ornamentation binder, preparation method includes the following steps:
(1), 69 parts of polyethylene, 15 parts of maleic anhydrides, 17 parts of silicone master batch HNC-MB50,5 parts of acrylic acid, 11 part third are weighed
Olefin(e) acid monooctyl ester, 0.6 part of azodiisobutyronitrile and 3 parts of acrylonitrile are added in reaction kettle, mixing speed 90r/min, maintain body
It is to react 30min under the conditions of 50 DEG C of temperature, temperature of reaction kettle is warming up to 81 DEG C of reaction 52min, temperature of reaction kettle is heated up
To 95 DEG C of heat preservation 1h, product washs 2 times through 500mL EtOH Sonicate, dry, and product is transferred in extruder, is squeezed in 178 DEG C
It is granulated out, obtains silicone modified polyethylene；
(2), 6 parts of acrylic acid, 3 parts of acrylonitrile, 18 parts of Isooctyl acrylate monomers, 2 parts of methyl methacrylates, 0.6 part of peroxide are weighed
Change benzoyl, 4 parts of maleic anhydrides and 1.5 parts of styrene to be added in reaction kettle, mixing speed 230r/min maintains body
It is to react 45min under the conditions of 83 DEG C of temperature, product is transferred in hydrothermal reaction kettle, maintaining hydrothermal temperature is 102 DEG C
Hydro-thermal reaction 2h, product wash 2 times through 500mL EtOH Sonicate, dry, obtain modified polyacrylate resin；
(3), 16 parts of 10X molecular sieves are weighed and 11 parts of mesoporous aluminum oxides are added in ball mill, drum speed 23r/
Min, barrel temperature are 40 DEG C of ball-milling reaction 45min, and product and 30 parts of tributyl 2-acetylcitrates, 13 parts of A-171 silane is even
Connection agent and 12 parts of tributyl citrate are added in hydrothermal reaction kettle, and maintenance hydrothermal temperature is 102 DEG C of hydro-thermal reactions
45min, product are dried in vacuo 6min through 500mL alcohol dipping 1min, in 45 DEG C, -0.06MPa to get modified acetyl lemon is arrived
Sour tributyl；
(4), 83 parts of polyethylene, 44 parts of terpene resins, 25 parts of natural rubbers, 25 parts of modified tributyl 2-acetylcitrates, 21 are weighed
Part maleic anhydride and 26 parts of modified polyacrylate resins are added in high-speed mixer, with high-speed mixer in temperature
179 DEG C of hybrid reaction 4min, with extruder 179 DEG C of extruding pelletizations of temperature to get arrive modified poly ethylene；
(5), 81 parts of modified poly ethylenes are weighed and 23 parts of silicone modified polyethylene are added in high-speed mixer, use high-speed mixer
In 180 DEG C of hybrid reaction 2min of temperature, with extruder in 182 DEG C of extruding pelletizations of temperature to get viscous to formaldehydeless polyethylene house ornamentation
Tie agent.
Embodiment 7
A kind of formaldehydeless polyethylene house ornamentation binder, preparation method includes the following steps:
(1), weigh 69 parts of polyethylene, 16.5 parts of maleic anhydrides, 19.3 parts of silicone master batch HNC-MB50,6.5 parts of acrylic acid,
15.3 parts of 2-ethyl hexyl acrylates, 0.9 part of azodiisobutyronitrile and 4.6 parts of acrylonitrile are added in reaction kettle, mixing speed 90r/
Min reacts 30min under the conditions of 50 DEG C of maintenance system temperature, temperature of reaction kettle is warming up to 86 DEG C of reaction 56min, will be reacted
Kettle temperature degree is warming up to 95 DEG C of heat preservation 1h, and product washs 2 times through 500mL EtOH Sonicate, dry, and product is transferred in extruder,
In 179 DEG C of extruding pelletizations, silicone modified polyethylene is obtained；
(2), 6 parts of acrylic acid, 4.9 parts of acrylonitrile, 20.5 parts of Isooctyl acrylate monomers, 2.8 parts of methyl methacrylates, 0.8 are weighed
Part benzoyl peroxide, 6.7 parts of maleic anhydrides and 1.9 parts of styrene are added in reaction kettle, mixing speed 230r/
Min reacts 45min under the conditions of 84 DEG C of maintenance system temperature, product is transferred in hydrothermal reaction kettle, maintains hydro-thermal reaction temperature
Degree is 107 DEG C of hydro-thermal reaction 2.7h, and product washs 2 times through 500mL EtOH Sonicate, dry, obtains modified polyacrylate tree
Rouge；
(3), 16.2 parts of 10X molecular sieves are weighed and 15.4 parts of mesoporous aluminum oxides are added in ball mill, drum speed is
23r/min, barrel temperature is 40 DEG C of ball-milling reaction 45min, by product and 30 parts of tributyl 2-acetylcitrates, 13.1 parts of A-171
Silane coupling agent and 14.3 parts of tributyl citrate are added in hydrothermal reaction kettle, and maintenance hydrothermal temperature is 107 DEG C of hydro-thermals
49min is reacted, product is dried in vacuo 6min through 500mL alcohol dipping 1min, in 45 DEG C, -0.06MPa to get modified acetyl is arrived
Tributyl citrate；
(4), 83 parts of polyethylene, 49 parts of terpene resins, 26.7 parts of natural rubbers, 30.2 parts of three fourths of modified acetyl tributyl citrate are weighed
Ester, 23.7 parts of maleic anhydrides and 29 parts of modified polyacrylate resins are added in high-speed mixer, use high-speed mixer
In 180 DEG C of hybrid reaction 5.5min of temperature, with extruder in 182 DEG C of extruding pelletizations of temperature to get arriving modified poly ethylene；
(5), 81 parts of modified poly ethylenes are weighed and 28.3 parts of silicone modified polyethylene are added in high-speed mixer, use mixed at high speed
Machine is in 182 DEG C of hybrid reaction 4.5min of temperature, with extruder in 184 DEG C of extruding pelletizations of temperature to get arriving formaldehydeless polyethylene man
Fill binder.
Embodiment 8
A kind of formaldehydeless polyethylene house ornamentation binder, preparation method includes the following steps:
(1), 69 parts of polyethylene, 15.2 parts of maleic anhydrides, 16 parts of silicone master batch HNC-MB50,6 parts of acrylic acid, 14 parts are weighed
2-ethyl hexyl acrylate, 0.7 part of azodiisobutyronitrile and 4 parts of acrylonitrile are added in reaction kettle, mixing speed 90r/min, are maintained
30min is reacted under the conditions of 50 DEG C of system temperature, temperature of reaction kettle is warming up to 82 DEG C of reaction 53min, by temperature of reaction kettle liter
Temperature to 95 DEG C of heat preservation 1h, product washs 2 times through 500mL EtOH Sonicate, dry, product is transferred in extruder, in 178 DEG C
Extruding pelletization obtains silicone modified polyethylene；
(2), 6 parts of acrylic acid, 4.5 parts of acrylonitrile, 17 parts of Isooctyl acrylate monomers, 2.2 parts of methyl methacrylates, 0.6 part are weighed
Benzoyl peroxide, 4.9 parts of maleic anhydrides and 1.7 parts of styrene are added in reaction kettle, mixing speed 230r/min,
45min is reacted under the conditions of 83 DEG C of maintenance system temperature, product is transferred in hydrothermal reaction kettle, maintenance hydrothermal temperature is
101 DEG C of hydro-thermal reaction 2.1h, product wash 2 times through 500mL EtOH Sonicate, dry, obtain modified polyacrylate resin；
(3), 14.3 parts of 10X molecular sieves are weighed and 13.3 parts of mesoporous aluminum oxides are added in ball mill, drum speed is
23r/min, barrel temperature is 40 DEG C of ball-milling reaction 45min, by product and 30 parts of tributyl 2-acetylcitrates, 12.6 parts of A-171
Silane coupling agent and 11.9 parts of tributyl citrate are added in hydrothermal reaction kettle, and maintenance hydrothermal temperature is 101 DEG C of hydro-thermals
44min is reacted, product is dried in vacuo 6min through 500mL alcohol dipping 1min, in 45 DEG C, -0.06MPa to get modified acetyl is arrived
Tributyl citrate；
(4), weigh 83 parts of polyethylene, 450 parts of terpene resins, 25 parts of natural rubbers, 26 parts of modified tributyl 2-acetylcitrates,
23.6 parts of maleic anhydrides and 27.8 parts of modified polyacrylate resins are added in high-speed mixer, are existed with high-speed mixer
177 DEG C of hybrid reaction 3.9min of temperature, with extruder 179 DEG C of extruding pelletizations of temperature to get arrive modified poly ethylene；
(5), 81 parts of modified poly ethylenes are weighed and 27 parts of silicone modified polyethylene are added in high-speed mixer, use high-speed mixer
In 181 DEG C of hybrid reaction 3.5min of temperature, with extruder in 182 DEG C of extruding pelletizations of temperature to get arriving formaldehydeless polyethylene house ornamentation
Binder.
Reference examples 1
In this reference examples, silicone modified polyethylene is not added, and other components and preparation method are same as Example 1.
Reference examples 2
In this reference examples, modified polyacrylate resin is not added, and other components and preparation method are same as Example 1.
Reference examples 3
In this reference examples, modified tributyl 2-acetylcitrate is not added, and other components and preparation method are same as Example 1.
Reference examples 4
The silicone modified polyethylene in common polythene alternate embodiment 1, other components and system are selected in this reference examples, in formula
Preparation Method is same as Example 1.
Reference examples 5
The modified polyacrylate resin in plain polypropylene acid ester resin alternate embodiment 1 is selected in this reference examples, in formula,
Other components and preparation method are same as Example 1.
Reference examples 6
The modification acetyl tributyl citrate three in common tributyl 2-acetylcitrate alternate embodiment 1 is selected in this reference examples, in formula
Butyl ester, other components and preparation method are same as Example 1.
Reference examples 7
The modified poly ethylene in common polythene alternate embodiment 1, other components and preparation side are selected in this reference examples, in formula
Method is same as Example 1.
The performance parameter of formaldehydeless polyethylene house ornamentation binder made from 1 embodiment 1 of table and reference examples 1~7
| Embodiment 1 | Reference examples 1 | Reference examples 2 | Reference examples 3 | Reference examples 4 | Reference examples 5 | Reference examples 6 | Reference examples 7 | |
| Adhesion strength/MPa | 3.2 | 2.8 | 2.3 | 1.3 | 2.6 | 2.0 | 1.8 | 0.2 |
The above is the preferred embodiment of the invention, it is noted that for those skilled in the art,
Under the premise of not departing from the inventive principle, several improvements and modifications can also be made, these improvements and modifications are also considered as the hair
Bright protection scope.
Claims (3)
1. a kind of preparation method of formaldehydeless polyethylene house ornamentation binder, it is characterised in that: including following raw material components: modified poly-
The mass parts ratio of ethylene and silicone modified polyethylene, the modified poly ethylene and silicone modified polyethylene is 81:21~29,
Wherein, the modified poly ethylene is by polyethylene, terpene resin, natural rubber, modified tributyl 2-acetylcitrate, maleic two
Acid anhydrides and modified polyacrylate resin reaction are made, the polyethylene, terpene resin, natural rubber, modified acetyl lemon
The mass parts ratio of sour tributyl, maleic anhydride and modified polyacrylate resin be 83:39~50:21~27:22~
31:17~25:23~30, the modification tributyl 2-acetylcitrate is by tributyl 2-acetylcitrate, 10X molecular sieve, A-171
Silane coupling agent, tributyl citrate and the reaction of mesoporous aluminum oxide are made, the tributyl 2-acetylcitrate, 10X point
The mass parts ratio of sub sieve, A-171 silane coupling agent, tributyl citrate and mesoporous aluminum oxide for 30:11~17:8~
14:9~15:8~16, the modified polyacrylate resin is by acrylic acid, acrylonitrile, Isooctyl acrylate monomer, metering system
Sour methyl esters, benzoyl peroxide, maleic anhydride and styrene reaction are made, and the acrylic acid, acrylonitrile, acrylic acid are different
Monooctyl ester, methyl methacrylate, benzoyl peroxide, maleic anhydride and styrene mass parts ratio be 6:2~5:14
~21:1~3:0.3~1:3~7:1~2, the silicone modified polyethylene is by polyethylene, maleic anhydride, silicone master batch
HNC-MB50, acrylic acid, 2-ethyl hexyl acrylate, azodiisobutyronitrile and acrylonitrile reactor are made, the polyethylene, maleic two
Acid anhydrides, silicone master batch HNC-MB50, acrylic acid, 2-ethyl hexyl acrylate, azodiisobutyronitrile and acrylonitrile mass parts ratio be 69:
9~17:14~20:2~7:9~16:0.3~1:2~5.
2. a kind of preparation method of formaldehydeless polyethylene house ornamentation binder according to claim 1, it is characterised in that: described
Formaldehydeless polyethylene house ornamentation binder is as made from following preparation method: (1), polyethylene, maleic anhydride, silicone is female
Grain HNC-MB50, acrylic acid, 2-ethyl hexyl acrylate, azodiisobutyronitrile and acrylonitrile are 69:9~17:14 according to mass parts ratio
~20:2~7:9~16:0.3~1:2~5 are added in reaction kettle, mixing speed 90r/min, and 50 DEG C of maintenance system temperature
Under the conditions of react 30min, temperature of reaction kettle is warming up to 78~87 DEG C of 45~60min of reaction, temperature of reaction kettle is warming up to 95
DEG C heat preservation 1h, product washs 2 times through 500mL EtOH Sonicate, dry, and product is transferred in extruder, is squeezed in 173~180 DEG C
It is granulated out, obtains silicone modified polyethylene；(2), by acrylic acid, acrylonitrile, Isooctyl acrylate monomer, methyl methacrylate, mistake
Benzoyl Oxide, maleic anhydride and styrene according to mass parts ratio be 6:2~5:14~21:1~3:0.3~1:3~
7:1~2 are added in reaction kettle, mixing speed 230r/min, react 45min under the conditions of 80~85 DEG C of maintenance system temperature,
Product is transferred in hydrothermal reaction kettle, maintenance hydrothermal temperature is 95~110 DEG C of 1~3h of hydro-thermal reaction, product warp
500mL EtOH Sonicate washs 2 times, dry, obtains modified polyacrylate resin；(3), by 10X molecular sieve and mesoporous three oxidation
Two aluminium are that 11~17:8~16 are added in ball mill according to mass parts ratio, drum speed 23r/min, barrel temperature 40
Product and mass parts ratio are tributyl 2-acetylcitrate, the A-171 silicon of 30:8~14:9~15 by DEG C ball-milling reaction 45min
Alkane coupling agent and tributyl citrate are added in hydrothermal reaction kettle, and maintenance hydrothermal temperature is 93~108 DEG C of hydro-thermal reactions
35~50min, product are dried in vacuo 6min through 500mL alcohol dipping 1min, in 45 DEG C, -0.06MPa to get modified acetyl is arrived
Tributyl citrate；(4), by polyethylene, terpene resin, natural rubber, modified tributyl 2-acetylcitrate, maleic anhydride
With modified polyacrylate resin according to mass parts ratio be 83:39~50:21~27:22~31:17~25:23~30 be added
Into high-speed mixer, with high-speed mixer in 175~181 DEG C of 2~6min of hybrid reaction of temperature, with extruder in temperature 177
~183 DEG C of extruding pelletizations to get arrive modified poly ethylene；(5), by modified poly ethylene and silicone modified polyethylene according to mass fraction
Than being added in high-speed mixer for 81:21~29, with high-speed mixer in 177~183 DEG C of 1~5min of hybrid reaction of temperature,
With extruder 179~185 DEG C of extruding pelletizations of temperature to get arrive formaldehydeless polyethylene house ornamentation binder.
3. a kind of preparation method of formaldehydeless polyethylene house ornamentation binder according to claim 1, it is characterised in that: described
The glass transition temperature of terpene resin is 30 DEG C.
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| CN113667419A (en) * | 2021-08-12 | 2021-11-19 | 烟台正海合泰科技股份有限公司 | Three-layer adhesive film and production method thereof |
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